JP2531731B2 - Chlorinated ethylene copolymer mixture - Google Patents

Description

TECHNICAL FIELD The present invention relates to a chlorinated ethylene copolymer mixture having excellent vulcanizability. More specifically, it not only has excellent vulcanizability, but also has good flexibility and compression set, and also has excellent adhesion to metal and synthetic fiber base materials, and also has excellent heat resistance. Chlorinated ethylene-based copolymer mixture.

[Conventional technology]

Chlorinated polyethylene, especially amorphous chlorinated polyethylene rubber, has a chemically saturated structure and is a crosslinked product (vulcanized product) based on a chlorine-containing polymer substance.
Has good physical properties such as weather resistance, flame resistance, chemical resistance, electrical characteristics and heat resistance, so it can be molded into wire coatings, electrical parts, hoses, building materials, automobile parts, packing, sheets, etc. Is used in the industrial field.

However, unlike a general-purpose rubber (for example, a rubber containing butadiene as a main component), this chlorinated polyethylene has a chemically saturated structure as described above, so that sulfur or a sulfur donor can be vulcanized as a vulcanizing agent. Have difficulty. Therefore, a method of crosslinking using an organic peroxide is generally used as a crosslinking agent. However, when a hose, a sheet, a tube, or the like is extruded and then crosslinked using a vulcanizing can generally used in the rubber industry, it is difficult to properly crosslink the resulting crosslinked product. Therefore, the crosslinked product obtained is inferior in tensile strength, heat resistance and the like. Furthermore, the adhesiveness to a metal or synthetic fiber (for example, nylon or polyester) base material is not good.

Therefore, it has been proposed to use sulfur or a sulfur donor for vulcanization (for example, JP-A-55-71742). Further, some of the present inventors have made it possible to vulcanize sulfur and / or a sulfur donor by further blending a thiourea compound, a metal salt of dithiocarbamate, and magnesium oxide and / or lead oxide as an acid acceptor. A vulcanizable chlorinated polyethylene-based composition that is possible and has excellent mechanical properties (for example, tensile strength) has been proposed (JP-A-61-209244).

[Problems to be Solved by the Invention]

However, as is clear by comparing FIG. 1 with this composition, the vulcanizability is not always satisfactory, and therefore the flexibility and compression set are not sufficient, and the heat resistance is also poor. There are drawbacks.

From the above, the present invention does not have these drawbacks (problems), that is, not only the vulcanizability required in the field of chlorinated polyethylene is extremely good, but also the tensile resistance and compression set are excellent. A chlorinated ethylene series that has excellent mechanical properties, good adhesion to metal and synthetic fiber substrates, and excellent heat resistance, hot water resistance, acid resistance, and alkali resistance. To obtain a polymer mixture.

[Means and Actions for Solving Problems]

According to the present invention, these problems are caused by: (A) melt flow index [measured according to JIS K7210, condition 4; hereinafter referred to as "MFR"] 0.1 to 100 g
/ 10 minutes, and the copolymerization ratio of α, β-unsaturated dicarboxylic acid and its anhydride is 0.5 to 25 mol% in total.
Which is a chlorinated product of an ethylene-based copolymer of at least ethylene and α, β-unsaturated dicarboxylic acid and / or its anhydride, wherein the chlorinated product has a chlorine content of 5 to 40% by weight, and Mooney 100 parts by weight of a chlorinated ethylene copolymer having a viscosity (ML _{1 + 4} , 100 ° C.) of 5 or more, (B) “benzothiazyl sulfenamide of a secondary amine represented by the general formula (I) (Hereinafter referred to as “sulfenamide compound”) 1.0 to 10.0 parts by weight, However, R ₁ and R ₂ may be the same or different and is a hydrocarbon group having at most 18 carbon atoms, but is a group having no substituent containing a hetero atom, or R ₁ and R ₂ and May be bonded to each other to form a hydrocarbon ring, or may be bonded via a hetero atom to form a heterocyclic ring. (C) A mercaptotriazine system represented by the general formula (II) 0.01 to 5.0 parts by weight of compound, (However, R ₃ is selected from the group consisting of a mercapto group and an amino group.) (D) A chlorinated ethylene copolymer composition comprising 1.0 to 15.0 parts by weight of a metal compound serving as an acid acceptor. it can. Hereinafter, the present invention will be specifically described.

(A) Chlorinated ethylene-based copolymer In producing the chlorinated ethylene-based copolymer used in the present invention, the ethylene-based copolymer which is a raw material contains at least ethylene and “α, β-unsaturated dicarboxylic acid and / or Or its anhydride "(hereinafter referred to as" comonomer (1) "). The copolymer may be a copolymer of ethylene and the comonomer (1). In addition to the ethylene and the comonomer (1), the copolymer comprises “an unsaturated carboxylic acid ester, an alkoxyalkyl acrylate and a vinyl ester” as a third copolymer component. A multi-component copolymer comprising a monomer selected from the group and having at least one double bond ”(hereinafter referred to as“ comonomer (2) ”) may be used.

 Among the comonomers (1), α, β-unsaturated dicarboxylic acids
The number of carbon atoms in an acid is usually at most 20, especially 4 to 16
Individual ones are preferred. As a representative example of the dicarboxylic acid
Is maleic acid, fumaric acid, itaconic acid, citracone
Acid, 3,6-endomethylene-1,2,3,6-tetrahydro-shi
Superphthalic acid (Nadic acid ).

Of the α, β-unsaturated dicarboxylic acid components of the present application, anhydrides of the aforementioned α, β-unsaturated dicarboxylic acids are preferred, and maleic anhydride is particularly preferred.

Among the comonomers (2), the unsaturated carboxylic acid ester usually has 4 to 40 carbon atoms, and particularly preferably 4 to 20 carbon atoms. As typical examples, those having good thermal stability such as methyl (meth) acrylate and ethyl (meth) acrylate are preferable.

Furthermore, the alkoxyalkyl acrylate usually has at most 20 carbon atoms. Further, an alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms) is preferable, and an alkoxy group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms).
4 pieces are desirable. Representative examples of preferred alkoxyalkyl acrylates include methoxyethyl acrylate, ethoxyethyl acrylate and butoxyethyl acrylate.

Also, the carbon number of vinyl ester is generally at most
20 (preferably 4 to 16). Representative examples of suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl piperate, and the like.

In the ethylene copolymer of the present invention, the copolymerization ratio of the comonomer (1) is 0.5 to 25 mol%, preferably 1.0 to 25 mol%, and particularly preferably 1.0 to 20 mol%. If an ethylene-based copolymer having a comonomer (1) copolymerization ratio of less than 0.1 mol% is used, the effect of the obtained chlorinated product is not exhibited. On the other hand, an ethylene-based copolymer having a content of more than 25 mol% has problems in cost and production when it is industrially produced.

In the present invention, the terpolymer composed of ethylene, the comonomer (1) and the comonomer (2) has no blocking during chlorination, and the reaction can be easily carried out. Furthermore, the obtained chlorinated ethylene-based copolymer is excellent in rubber elasticity and heat resistance, which is preferable.

Further, the copolymerization ratio of the comonomer (2) is
In terms of cost, it is generally 25 mol% at most, and 0.5 to 2
5 mol% is preferable, and 1.0 to 25 mol% is particularly preferable.

The MFR of the ethylene copolymer is 0.1 to 100 g / 10 minutes, preferably 0.5 to 100 g / 10 minutes, particularly 1.0 to 100 g / min.
10 minutes is preferred. If an ethylene copolymer having an MFR of less than 0.1 g / 10 minutes is used, the resulting chlorinated ethylene copolymer has poor moldability and kneading properties. On the other hand, 100g / 10
If an ethylene-based copolymer exceeding the amount is used, the mechanical properties of the resulting chlorinated ethylene-based copolymer will be poor.

In order to produce the chlorinated ethylene copolymer of the present invention,
The ethylene copolymer is suspended in an aqueous medium. In order to maintain this aqueous suspension state, it is preferable to add a small amount of an emulsifying agent or suspending agent. In this case, if necessary, a radical generator such as benzoyl peroxide, azobisisobutyronitrile and hydrogen peroxide, a defoaming agent such as light silicone oil, and other additives may be added.

In producing the chlorinated ethylene copolymer of the present invention, it is desirable to chlorinate it in the above-mentioned aqueous suspension by the following three methods.

The first method is at a temperature at least 25 ° C lower than the melting point of the ethylene-based copolymer used in the first step, but chlorinates 20 to 60% of the total chlorination amount at a temperature higher than 50 ° C, In this step, the remaining chlorination is carried out at a temperature higher than the chlorination temperature in the first step by 10 ° C. or more, but lower than the melting point of the ethylene-based copolymer by 5 to 15 ° C.

In the second method, the temperature is at least 25 ° C lower than the melting point of the ethylene-based copolymer used in the first step, but at a temperature higher than 50 ° C, the total chlorination amount is 20 to 60 ° C.
Is chlorinated, and in the second step, the temperature is raised to a temperature 1 to 7 ° C. higher than the melting point of the ethylene-based copolymer, and annealed at this temperature for 10 to 60 minutes without introducing chlorine. It is a method of performing the remaining chlorination at a temperature 2 to 25 ° C. lower than the melting point of the ethylene-based copolymer.

Furthermore, the third method is a temperature at least 25 ° C. lower than the melting point of the ethylene copolymer used in the first step, but at a temperature higher than 50 ° C., the total chlorination amount is 20 to
60% is chlorinated, and in the second stage the temperature is 10 ° C. or more higher than the chlorination temperature in the first stage, but the remaining chlorination temperature is 5 to 15 ° C. lower than the melting point of the ethylene copolymer. At least 30% of the amount, chlorinating by this stage 60-90% of the total chlorination amount, and then in a third stage at a temperature below the melting point of the ethylene-based copolymer but 2 ° C. below the melting point The following is a method of performing chlorination at a low temperature.

The chlorine content of the chlorinated ethylene copolymer used in the present invention thus obtained is 5 to 45% by weight.
(Preferably 5 to 40% by weight, suitably 10 to 35% by weight). If the chlorine content of this chlorinated ethylene-based copolymer is less than 5% by weight, there is a problem in recovering and purifying the obtained chlorinated ethylene-based copolymer. Moreover, flame resistance is poor. On the other hand, a chlorinated ethylene-based copolymer produced when it exceeds 45% by weight is not preferable because it is significantly deteriorated in thermal stability and heat resistance.

The Mooney viscosity at a temperature of 100 ° C. is 5 points or more for a large rotor, preferably 5 to 150 points, and particularly preferably 10 to 150 points.

Further, the melt flow index (measured according to JIS K-7210 under the condition of 8 and hereinafter referred to as “FR”) is generally 1 to 100 g / 10 minutes, preferably 3 to 50 g / 10 minutes,
Particularly, 5 to 30 g / 10 minutes is preferable.

(B) Sulfenamide Compound The general formula of the sulfenamide compound used in the present invention is represented by the following formula [Formula (1)].

However, R ₁ and R ₂ may be the same or different and each has at most 18 carbon atoms (preferably 1 to 15 and preferably 1 to 15).
12) hydrocarbon groups having no substituent containing a heteroatom, or R ₁ and R ₂ may combine with each other to form a hydrocarbon ring, and further a heteroatom May be bonded via to form a heterocyclic ring.

This hydrocarbon group is selected from an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, and preferable specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group and a benzyl group.

Specific examples of the secondary amine forming the sulfenamide compound include di-ethylamine, di-propylamines, di-butylamines, di-hexylamines, di-octylamines, di-laurylamines. , Di-cyclohexylamine, piperidine, pipecoline, morpholine, piperazine and the like. 2-Mercaptobenzothiazole is preferable as the mercapto compound which is one of the components for forming the sulfenamide compound.
That is, representative examples of preferable sulfenamide compounds include N, N-diisopropyl 2-benzothiazyl sulfenamide, N, N-di-n-butyl-2-benzothiazyl sulfenamide, Examples thereof include N, N-dicyclohexyl-2-benzothiazylsulfenamide and N-oxy-diethylene 2-benzothiazylsulfenamide.

(C) Mercaptotriazine Compound Further, the mercaptotriazine compound used in the present invention is used as a vulcanizing agent or vulcanization accelerator in the rubber industry, and has a general formula represented by the following formula ((II) ] Is shown.

(However, R ₃ is selected from the group consisting of a mercapto group and an amino group.) In the formula (II), the amino group in R ₃ may have a hydrocarbon group having at most 20 carbon atoms.

Typical examples of the mercaptotriazine-based compound include 1,3,5-trithiocyanuric acid, 1-hexylamino-3,5-dimethylcaptotriazine, 1-diethylamino-3,5-dimercaptotriazine, 1-cyclohexylamino- Examples thereof include 3,5-dimercaptotriazine. This compound is described in detail in JP-A-59-10099.

(D) Metal compound Further, examples of the metal compound used as the acid acceptor in the present invention include oxides, hydroxides, carbonates, carboxylates, silicates and borates of metals of Group II of the periodic table. Acid salts and phosphites and oxides of metals of group IVa of the periodic table,
Examples thereof include basic carbonates, basic carboxylates, basic phosphites, basic sulfites and tribasic sulfates.

Representative examples of the metal compound include magnesium oxide (magnesia), magnesium hydroxide, magnesium carbonate, barium hydroxide, magnesium carbonate, barium carbonate, calcium oxide (quick lime), calcium hydroxide (slaked lime), calcium carbonate, and silicic acid. Calcium, calcium stearate, calcium phthalate, magnesium phosphite, calcium phosphite, zinc oxide (zinc white), tin oxide, litharge, leadtan, white lead, dibasic lead phthalate, dibasic lead carbonate, Examples include lead stearate, basic lead phosphite, basic tin phosphite, basic lead sulfite, and tribasic lead sulfate.

The average particle size of the metal compound is usually 0.1 to 100 μm,
0.2 to 110 μm is desirable, and 0.5 to 50 μm is particularly preferable. If a metal compound having an average particle size of less than 0.1 μm is used, scattering occurs during kneading, which causes a problem in handling. On the other hand, if the particle size exceeds 100 μm, secondary aggregation easily occurs and it is difficult to uniformly disperse the particles.

In producing the chlorinated ethylene-based copolymer mixture of the present invention, the chlorinated ethylene-based copolymer is mixed with the above-mentioned sulfenamide-based compound and a metal compound to be an acid acceptor to obtain a desired mixture. Although they can be obtained, they may be further blended with other vulcanization accelerators.

(E) Other Vulcanization Accelerators Other vulcanization accelerators used in the present invention are generally widely used as vulcanization accelerators in the rubber industry. Typical examples thereof are classified into thiazole type, imidazoline type, dithiocarbamate type, thiuram type, xanthate type, guanidine type and aldehyde / amine type. Further, nucleophiles such as amines described in the above-mentioned publication pages 64 to 67 and phosphorus compounds described in the publications pages 64 and 170 to 173 are also vulcanized. Can be used as a promoter. Representative examples of these vulcanization accelerators are described in the specification of JP-A-59-15440.

(F) Mixing ratio The mixing ratio of the other mixing components to 100 parts by weight of the chlorinated ethylene copolymer is as follows.

The sulfenamide-based compound is 1.0 to 10.0 parts by weight, preferably 2.0 to 10.0 parts by weight, and particularly preferably 3.0 to 10.0 parts by weight. If the mixing ratio of the sulfenamide compound is less than the lower limit, the vulcanizability of the resulting mixture will be insufficient. On the other hand, even if the content exceeds the upper limit, the vulcanizability cannot be further improved. Further, in the mercaptotriazine-based compound, 0.01 to 5.0 parts by weight, 0.02 to 1.5
Part by weight is preferable, and 0.1 to 4.0 parts by weight is particularly preferable.
If the mixing ratio of the mercaptotriazine-based compound is 0.01 parts by weight, the crosslinking will not be tight and it will be difficult to make the crosslinking tight. On the other hand, if the amount is more than 5.0 parts by weight, the resulting cross-linked product has poor tearability at high temperature. Furthermore, the mixing ratio of the metal compound is 1.0 to 15.0 parts by weight, and 2.0 to
15.0 parts by weight is preferable, and 3.0 to 12.0 parts by weight is particularly preferable. When the mixing ratio of the metal compound is less than 1.0 part by weight, the chlorinated ethylene copolymer causes a dehydrochlorination reaction. On the other hand, even if the amount is more than 15.0 parts by weight, not only the dehydrochlorination reaction cannot be prevented, but also the processability deteriorates and the rubber strength of the obtained vulcanizate decreases.

In addition, when the above-mentioned other vulcanization accelerators are blended, the mixing ratio is generally at most 10.0 parts by weight.

(G) Mixing method, vulcanization method, molding method, etc. The mixture of the present invention can be obtained by uniformly blending the above substances, but further, fillers, plasticizers, oxygen generally used in the rubber industry. Additives such as a stabilizer against ozone, heat and light (ultraviolet light), a lubricant and a coloring agent may be added according to the intended use of the mixture.

To obtain the mixture of the present invention, a mixing method which is commonly used in the rubber industry may be applied. In producing this mixture, it is important that the chlorinated ethylene copolymer is essentially not vulcanized. For this reason, mixing is generally carried out at room temperature to 100 ° C.

The mixture thus obtained is formed into a desired shape using an extrusion molding machine, an injection molding machine, a compression molding machine or the like generally used in the general rubber industry.

Vulcanization is usually performed during molding in the temperature range of 100 to 200 ° C.
Alternatively, it is heated by a steam can, an air bath, or the like. The vulcanization time depends on the vulcanization temperature, but is generally 0.
5 to 120 minutes.

Examples and Comparative Examples Hereinafter, the present invention will be described in more detail with reference to Examples.

In Examples and Comparative Examples, tensile strength (hereinafter, referred to as “T _B ”) and elongation (hereinafter, referred to as “E _B ”) were measured using a Schooper tester. The hardness test was performed using a Shore A hardness meter. Further, in the compression set test, the sample is compressed to a compression of 25%, the compression is maintained at a constant load, and then left in a heat aging tester at 100 ° C. for 22 hours. Thereafter, the load was removed, the sample was allowed to stand in a constant temperature room at a temperature of 23 ° C. and a humidity of 60% for 30 minutes, and its strain rate was measured. In the vulcanization test, a disk rheometer (ODR-100 type) tester was used and the temperature was 150 ° C, the amplitude was 3 degrees, and the full scale was 100 Kg / c.
The measurement was performed for 1 hour at m ² , and the vulcanization curve at that time was measured. In the adhesion test, a specimen (thickness 4 mm) of each chlorinated ethylene-based copolymer mixture was applied to an aluminum plate (about 1 m thick).
m), and peeled in the direction of 90 degrees under the condition of a tensile speed of 50 mm according to JIS K6301 to evaluate.

The types and physical properties of the chlorinated ethylene copolymers, sulfenamide compounds, mercaptotriazine compounds, metal compounds and other vulcanization accelerators used in Examples and Comparative Examples are shown below.

[(A) Chlorinated ethylene copolymer]

As a chlorinated ethylene copolymer, MF in aqueous suspension
R is 100g / 10 minutes, and the melting point is 108 ℃ ethylene-methyl methacrylate-maleic anhydride terpolymer (copolymerization ratio of methyl methacrylate 18.5 mol%, copolymerization ratio of maleic anhydride 1.5 mol% (Hereinafter referred to as "EMMA") was charged and chlorinated with stirring at a temperature range of 50 to 85 ° C until the chlorine content of the copolymer reached 15.2% by weight (first stage chlorination). Then, set the reaction system to 109
The temperature was raised to about 118 ° C., and introduction of chlorine was stopped in this temperature range, and annealing was performed for 30 minutes (second stage annealing). Then, the reaction system is cooled and chlorinated in the temperature range of 88 to 106 ° C until the chlorine content becomes 35.1% by weight (third stage chlorination), and the obtained Mooney viscosity (ML
_{1 + 4} , 100 ° C.) 32.5 chlorinated ethylene-based copolymer [FR 10.2 g / 10 minutes, hereinafter referred to as “ClEMMA (A)”] and the above EMMA 10 Kg were charged in the same manner as above, while stirring 50
The chlorine content of the copolymer is 1 in the temperature range of -80 ° C.
Chlorinated to 8.1 wt% (first stage chlorination).
Then, the reaction system was heated to 93 to 103 ° C., and chlorinated in this temperature range until the chlorine content reached 30.0% by weight (second stage chlorination). Then chlorinated in the temperature range of 118-120 ℃ until the chlorine content becomes 35.1% by weight (third stage chlorination), and Mooney viscosity (ML _{1 + 4} , 100 ℃) is 34.5. Combined (FR 10.8g / 10 minutes, below `` ClEMM
A (B) "].

[(B) Sulfenamide Compound]

As the sulfenamide compound, N, N-di-n-butyl-2-benzothiazylsulfenamide [hereinafter referred to as "amide (a)"] was used.

[(C) Mercaptotriazine Compound]

As the mercaptotriazine compound, 1,3,5-mercapto-S-triazine [hereinafter referred to as "azine (1)"] was used.

[(D) Metal compound]

As the metal compound, magnesium oxide having an average particle size of 1.0 μm (hereinafter, referred to as MgO) and lead tin having an average particle size of 1.5 μm (hereinafter, referred to as “Pb ₃ O ₄ ”) were used.

[(E) Other vulcanization accelerators]

Further, tetramethylthiuram disulfide (hereinafter referred to as "TT") was used as another vulcanization accelerator.

Examples 1 to 6 and Comparative Examples 1 to 7 The formulations whose amounts and types are shown in Table 1 were prepared at room temperature (about 20 ° C) using an open roll.
The mixture was kneaded for a minute to form a sheet. Using a compression molding machine, the temperature of 160 ° C and the pressure of each of the obtained sheet materials were 200
A vulcanized product was produced while vulcanizing at Kg / cm ² for 30 minutes. The obtained vulcanizates were tested for tensile strength, elongation, hardness and compression set. Table 2 shows the results.
Further, a vulcanization test was conducted using a sheet obtained by an open roll. FIG. 1 shows the results.

Comparative Example 8 Instead of ClEMMA (A) used in Example 1, the molecular weight was about 200,000 and the density was 0.950 g / cm ^{3 in} advance.
Mooney viscosity (MS _{1 + 4} , 100
A sheet was formed by kneading in the same manner as in Example 1 except that chlorinated polyethylene having a chlorine content of 35.2% by weight was used. The obtained sheet was vulcanized in the same manner as in Example 1 to produce a vulcanized product. The obtained vulcanizates were tested for tensile strength, elongation, hardness and compression set. The results are shown in Table 2. Further, the vulcanization test was performed in the same manner as in Example 1. The results are shown in FIG.

In Comparative Example 3, dehydrochlorination was caused during vulcanization, and the vulcanized product could not be formed into a sheet.

The chlorinated ethylene-based copolymer mixtures obtained in all the examples were subjected to an adhesion test. In each case, the specimen of the chlorinated ethylene copolymer mixture was cut.

Furthermore, Examples 1 and 2 and Comparative Examples 1 and 8
FIG. 1 shows the cross-linking curves of the mixture (kneaded material) obtained as above as a, b, c and d, respectively.

From the results of the above Examples and Comparative Examples, the vulcanizable chlorinated ethylene copolymer mixture obtained according to the present invention is:
It is clear that not only the tensile strength (T _B ) and the compression set are excellent, but also a good vulcanization curve is obtained from the rheometer curve.

〔The invention's effect〕

As is clear from FIG. 1, the chlorinated ethylene copolymer mixture obtained by the present invention not only has excellent vulcanizability than ordinary chlorinated polyethylene, but also exhibits the following effects.

(1) Good ozone resistance.

(2) Excellent resilience.

(3) Good flame retardancy.

(4) It has excellent weather resistance and durability.

(5) Good tearability and other mechanical strength.

(6) It has excellent oil resistance.

(7) Heat resistance and low temperature properties are also good.

(8) Excellent adhesion to metals and the like.

The chlorinated ethylene copolymer mixture of the present invention has such excellent properties as described above, so that it can be used in various fields. Typical application examples are shown below.

(1) Various parts for automobiles (for example, hoses and tubes) (2) Covering materials for electric wires (3) Adhesives (4) Parts for electronic equipment, electric equipment, etc.

[Brief description of drawings]

FIG. 1 is a cross-sectional curve diagram of each mixture obtained in Examples 1 and 2 and Comparative Examples 1 and 8 measured using a disc rheometer. In this figure, the vertical axis indicates torque (Kg · cm), and the horizontal axis indicates crosslinking time (minutes). It should be noted that a, b, c and d represent the cross-linking curves of the mixtures obtained in Example 1, Example 2, Comparative Example 1 and Comparative Example 8, respectively.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical indication (C08K 13/02 (C08K 13/02 3:10 3:10 5:47 5:47 5: 378 ) 5: 378) (72) Inventor Toshiyuki Iwashita, Oita City, Oita Prefecture 2 Nakanozu, Showa Denko Co., Ltd. Oita Laboratory (56) Reference JP-A-1-234449 (JP, A)

Claims (1)

(57) [Claims] (A) a melt flow index of 0.1 to 1
00g / 10 minutes, and the copolymerization ratio of α, β-unsaturated dicarboxylic acid and its anhydride is 0.5 to 25 in total.
Mole percent of at least ethylene and a chlorinated ethylene copolymer of an α, β-unsaturated dicarboxylic acid and / or an anhydride thereof, wherein the chlorine content of the chlorinated product is 5 to 5.
100 parts by weight of a chlorinated ethylene copolymer having a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 5% or more, 40% by weight, (B) a secondary amine represented by the general formula (I) Benzothiazyl sulfenamide 1.0 to 10.0 parts by weight, However, R ₁ and R ₂ may be the same or different and is a hydrocarbon group having at most 18 carbon atoms, but is a group having no substituent containing a hetero atom, or R ₁ and R ₂ and May be bonded to each other to form a hydrocarbon ring, or may be bonded via a hetero atom to form a heterocyclic ring. (C) A mercaptotriazine system represented by the general formula (II) Compound 0.01-5.0 parts by weight, (However, R ₃ is selected from the group consisting of a mercapto group and an amino group) and (D) a chlorinated ethylene copolymer mixture comprising 1.0 to 15.0 parts by weight of a metal compound serving as an acid acceptor.